Fluorine-containing wastewater adsorption treatment device, adsorption material and preparation method of adsorption material

Abstract

The invention provides a fluorine-containing wastewater adsorption treatment device, an adsorption material and a preparation method of the adsorption material. The fluorine-containing wastewater adsorption treatment device comprises: a housing; and the interior of the shell is rotationally connected with a treatment barrel, a filter screen is installed on the treatment barrel, and a discharging groove is formed in the bottom of the treatment barrel. According to the fluorine-containing wastewater adsorption treatment device, the adsorption material and the preparation method thereof provided by the invention, the fluorine-containing wastewater and the adsorption material are put into the treatment barrel together for reaction, so that fluorine elements in the fluorine-containing wastewater are adsorbed into the adsorption material to generate precipitates, and after standing and precipitating, the fluorine elements in the fluorine-containing wastewater are separated out; wastewater and sediments can be separated along with contraction of the displacement part, and the sediments can be discharged after the displacement part contracts again, so that multiple functions of reaction, sedimentation and discharging are integrated, the use cost is greatly reduced, the occupied area is reduced, discharging is facilitated, the labor amount of workers is reduced, meanwhile, switching among different states is achieved, and the working efficiency is improved. The operation is simple and convenient, and the multifunctional use effect is achieved.

Description

Technical Field

[0001] The present invention relates to the field of brine treatment, and particularly to an adsorption treatment device for fluorine-containing wastewater, an adsorption material and a preparation method thereof. Background Art

[0002] With the development of modern industry, a large amount of fluorine-containing brine is generated during the production processes of mining and metallurgy industries. These brines usually contain a large amount of fluorine element in the form of fluoride ions. High-concentration fluorine is harmful to the environment and human health, so it must be removed. Direct discharge of fluorine-containing wastewater will pollute the environment, causing poisoning of humans and livestock in the surrounding areas and leading to endemic fluorosis. Direct use inside will cause system disorders or even breakdowns, corrosion of evaporators, and other problems.

[0003] The basic principle of the adsorption method is that F- in water is adsorbed onto the surface of a solid adsorbent, bonding with the surface of the adsorbent or simply adsorbed on the surface through relatively weak intermolecular forces. The defluorination effect of this method is mainly restricted by the type of adsorbent.

[0004] In the prior art, a large number of devices are used for adsorbing fluorine-containing wastewater. Generally, reaction tanks, sedimentation tanks, filtration devices and other devices are required. The structure is complex. A large number of devices not only increase the cost, but also require a larger floor area. Moreover, after adsorption, the sediment needs to be shoveled by workers, and the cleaning is rather troublesome.

[0005] Therefore, it is necessary to provide an adsorption treatment device for fluorine-containing wastewater to solve the above technical problems. Summary of the Invention

[0006] The present invention provides an adsorption treatment device for fluorine-containing wastewater, which solves the problems that a large number of devices not only increase the cost, but also require a larger floor area, and after adsorption, the sediment needs to be shoveled by workers and the cleaning is rather troublesome.

[0007] To solve the above technical problems, the adsorption treatment device for fluorine-containing wastewater provided by the present invention includes: a housing;

[0008] A treatment barrel is rotatably connected inside the housing. The treatment barrel is used to hold fluorine-containing wastewater and put in an adsorption material to cause an adsorption reaction between the fluorine-containing wastewater and the adsorption material. A filter screen is installed on the treatment barrel, and a discharge chute is installed at the bottom of the treatment barrel. A drainage trough and an opening trough are arranged on the left side of the housing. A partition is fixedly connected inside the housing, and a sliding sleeve is slidably connected to the partition;

[0009] A displacement member is fixedly connected to the bottom of the housing. The top of the displacement member is fixedly connected to a connecting plate. A support sleeve is fixedly connected to the connecting plate. A cylinder is installed at the bottom of the housing. A sliding block is slidably connected inside the cylinder. A first elastic member is installed at the bottom of the sliding block. A connecting rod is installed at the top of the sliding block. An engaging block is fixedly connected to the outer surface of the connecting rod. The top of the connecting rod penetrates through the connecting plate and is installed with a sealing plate. The sealing plate abuts against the discharge chute to close the discharge chute.

[0010] Preferably, a support frame is fixedly connected to the top of the housing. A stirring rod is fixedly connected to the bottom of the support frame. The stirring rod extends into the treatment barrel. Multiple groups of stirring blades are arranged on the outer surface of the stirring rod. A driving motor is installed on the housing. A transmission assembly is installed between the driving motor and the treatment barrel. The driving motor drives the treatment barrel to rotate through the transmission assembly to achieve stirring. During stirring, the sliding sleeve covers the outer surface of the filter screen to block the filter screen.

[0011] Preferably, the transmission assembly is two mutually meshing gears. One of the gears is installed on the output shaft of the driving motor, and the other gear is installed on the outer surface of the treatment barrel.

[0012] Preferably, a cavity is formed inside the stirring rod. Telescopic rods are slidably connected inside each of a group of the stirring blades. A second elastic member is sleeved on the outer surface of each telescopic rod. One end of the telescopic rod extends into the cavity. A scraping plate is installed at the other end of the telescopic rod. First inclined surfaces are arranged at opposite ends of the two telescopic rods. An auxiliary rod is fixedly connected to the top of the sealing plate. The auxiliary rod extends into the cavity. A moving block is installed at the top of the auxiliary rod. Second inclined surfaces are arranged symmetrically at the bottom of the moving block.

[0013] Preferably, a water collection tank and a suction pump are fixedly connected to the right side of the housing. A first connecting pipe communicates between the water collection tank and the inlet of the suction pump. The outlet of the suction pump is communicated with a second connecting pipe. The second connecting pipe penetrates through the housing and extends into the housing. A spray head is installed on the second connecting pipe. A conduit communicates between the drainage trough and the water collection tank.

[0014] An adsorption material is added to the fluorine-containing wastewater adsorption treatment device to achieve the treatment of fluorine-containing wastewater. It is prepared from carboxymethyl chitosan and amino-functionalized magnetic nanoparticles.

[0015] A preparation method of an adsorption material is used to prepare the adsorption material, including:

[0016] S1. Prepare carboxymethyl chitosan, and the steps are as follows:

[0017] S11. Place chitosan in a three-necked flask, add an organic solvent to dissolve and stir.

[0018] S12. Slowly add sodium hydroxide solution using a dropping funnel, and stir under constant temperature water bath for alkalization.

[0019] S13. Dissolve chloroacetic acid in an organic solvent, slowly add it to the alkalized chitosan solution, and raise the temperature to continue stirring.

[0020] S14. Add glacial acetic acid to adjust the pH, pour the reaction solution into absolute ethanol and stir.

[0021] S15. Centrifuge and separate the precipitate, wash and dry it to obtain carboxymethyl chitosan.

[0022] S2. Prepare amino-functionalized magnetic nanoparticles, and the steps are as follows:

[0023] S21. Dissolve substances containing divalent iron ions and trivalent iron ions in deionized water respectively to prepare solutions, and place them in a three-necked flask.

[0024] S22. Pass nitrogen to exhaust air, and stir vigorously under constant temperature water bath.

[0025] S23. Quickly add ammonia water using a dropping funnel, and continue stirring to obtain black Fe3O4 nanoparticles.

[0026] S24. Separate the Fe3O4 nanoparticles with a magnet, and wash them with deionized water until neutral.

[0027] S25. Disperse the washed Fe3O4 nanoparticles in absolute ethanol, and add a silane coupling agent or an amino acid substance.

[0028] S26. Carry out a reflux stirring reaction in a constant temperature water bath.

[0029] S27. Separate the amino-functionalized magnetic nanoparticles with a magnet, and wash them with absolute ethanol.

[0030] S3. Prepare a carboxymethylated chitosan-based magnetic adsorbent, and the steps are as follows:

[0031] S31. Dissolve the above-prepared carboxymethyl chitosan in deionized water to prepare a solution, slowly add it to the solution prepared with an aluminum source substance, and stir evenly.

[0032] S32. Add the above-prepared amino-functionalized magnetic nanoparticles, and ultrasonically obtain a uniformly mixed solution.

[0033] S33. Dissolve genipin in deionized water to prepare a solution, slowly add it to the above mixed solution, and stir under constant temperature water bath.

[0034] S34. Add an alkaline solution to adjust the pH of the mixed solution, and continue stirring.

[0035] S35. Prepare a solution of polyethyleneimine with a mass fraction of 2%, add it to the above mixed solution and stir.

[0036] S36. Add glutaraldehyde with a mass fraction of 25% to the above mixed solution and stir at room temperature.

[0037] S37. Wash the reaction product repeatedly with deionized water until the pH of the washing solution reaches neutral. After each washing, separate the product with a magnet.

[0038] S38. Dry the washed product to a constant weight to obtain a carboxymethylated chitosan-based magnetic adsorbent, i.e., the adsorbent material.

[0039] Preferably, in S11, the organic solvent is one of isopropanol, methanol, ethanol, and acetone; in S12, the concentration of the sodium hydroxide solution is 40%-60%, the water bath temperature is 30-50°C, and the alkalization time is 1-2 h; in S13, the organic solvent is the same as that in S11, heat up to 60-80°C, and the stirring time is 4-6 h; in S14, the pH is neutral; in S15, the centrifugation speed is 4000-6000 r / min, the centrifugation time is 10-30 min, and the washing is carried out 3 times with absolute ethanol.

[0040] Preferably, in S21, the divalent iron ion substance is FeSO4·7H2O, and the trivalent iron ion substance is FeCl3·6H2O; in S22, the temperature is 80-100°C, and the stirring time is 30-60 min; in S23, the stirring time is 30-60 min; in S25, the silane coupling agent is one of γ-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and the amino acid substance is lysine; in S26, the temperature is 60-80°C, and the stirring time is 6-8 h; in S27, the washing is carried out 3 times with absolute ethanol.

[0041] Preferably, in S31, the aluminum source substance is one of aluminum nitrate nonahydrate and aluminum chloride; in S32, the ultrasonic time is 30-60 min; in S33, the constant temperature is 40-60°C, and the stirring time is 4-6 h; in S34, the alkaline solution is 1 mol / L sodium hydroxide solution, the pH is 8-9, and the stirring time is 6-8 h; in S35, the stirring time is 1-2 h; in S36, the stirring time is 6-8 h; in S38, dry in a vacuum environment, the temperature is 60-80°C, and the time is 60-90 min.

[0042] Compared with the related technologies, the fluorine-containing wastewater adsorption treatment device, adsorption material and preparation method thereof provided by the present invention have the following beneficial effects:

[0043] The present invention provides a fluorine-containing wastewater adsorption treatment device. By putting the fluorine-containing wastewater and the adsorption material into the treatment barrel for reaction together, the fluorine element in the fluorine-containing wastewater is adsorbed into the adsorption material to generate a precipitate. After standing and settling, as the displacement member shrinks, the wastewater and the precipitate can be separated. Another shrinkage can discharge the precipitate. It integrates multiple functions of reaction, precipitation and discharging, greatly reducing the use cost, reducing the floor area, facilitating discharging, reducing the labor intensity of the staff, realizing the conversion between different states at the same time, with simple and convenient operation and the effect of multi-functional use. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 is a schematic structural diagram of the first embodiment of the fluorine-containing wastewater adsorption treatment device provided by the present invention;

[0045] Figure 2 is Figure 1 a schematic cross-sectional view of the shown housing;

[0046] Figure 3 is Figure 2 a schematic enlarged view of part A shown;

[0047] Figure 4 is Figure 2 a schematic cross-sectional view of the shown stirring rod;

[0048] Figure 5 is a usage state diagram of the fluorine-containing wastewater adsorption treatment device. Among them, (5a) is a schematic diagram in the stirring state, (5b) is a schematic diagram in the solid-liquid separation state, (5c) is a schematic diagram in the discharging state, and (5d) is a schematic diagram when cleaning the filter screen;

[0049] Figure 6 is a schematic structural diagram of the second embodiment of the fluorine-containing wastewater adsorption treatment device provided by the present invention;

[0050] Figure 7 is Figure 6 a schematic cross-sectional view of the shown housing;

[0051] Figure 8 is a flowchart of the preparation method of the adsorption material provided by the present invention.

[0052] Reference numerals in the figures: 1, outer shell; 2, treatment barrel; 3, filter screen; 4, discharge chute; 5, drainage trough; 6, opening groove; 7, partition board; 8, sliding sleeve; 9, support frame; 10, stirring rod; 11, stirring blade; 12, drive motor; 13, transmission assembly; 14, displacement member; 15, connecting plate; 16, support sleeve; 17, cylinder; 18, sliding block; 19, first elastic member; 20, connecting rod; 21, connecting block; 22, sealing plate; 23, cavity; 24, telescopic rod; 25, second elastic member; 26, scraping plate; 27, first inclined surface; 28, auxiliary rod; 29, moving block; 30, second inclined surface; 31, water collecting tank; 32, suction pump; 33, first connecting pipe; 34, second connecting pipe; 35, spray head; 36, conduit. Specific implementation manner

[0053] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0054] The first embodiment

[0055] Please refer to Figures 1-5 wherein Figure 1 is a schematic structural diagram of the first embodiment of the fluorine-containing wastewater adsorption treatment device provided by the present invention; Figure 2 is Figure 1 a schematic cross-sectional view of the outer shell shown in Figure 3 is Figure 2 an enlarged schematic view of part A shown in Figure 4 is Figure 2 a schematic cross-sectional view of the stirring rod shown in Figure 5 is a usage state diagram of the fluorine-containing wastewater adsorption treatment device. Among them, (5a) is a schematic diagram in the stirring state, (5b) is a schematic diagram in the solid-liquid separation state, (5c) is a schematic diagram in the discharging state, and (5d) is a schematic diagram when cleaning the filter screen. The fluorine-containing wastewater adsorption treatment device includes: an outer shell 1;

[0056] The treatment barrel 2 is rotatably connected inside the outer shell 1. The treatment barrel 2 is used to hold fluorine-containing wastewater and put in an adsorbent material to enable an adsorption reaction between the fluorine-containing wastewater and the adsorbent material. A filter screen 3 is installed on the treatment barrel 2, a discharge chute 4 is installed at the bottom of the treatment barrel 2, a drainage trough 5 and an opening groove 6 are arranged on the left side of the outer shell 1, a partition board 7 is fixedly connected inside the outer shell 1, and a sliding sleeve 8 is slidably connected to the partition board 7;

[0057] A displacement member 14 is fixedly connected to the bottom of the outer shell 1. The top end of the displacement member 14 is fixedly connected to a connecting plate 15. A support sleeve 16 is fixedly connected to the connecting plate 15. The support sleeve 16 is used to support the sliding sleeve 8 to block the filter screen 3. A cylinder 17 is installed at the bottom of the outer shell 1. A sliding block 18 is slidably connected inside the cylinder 17. A first elastic member 19 is installed at the bottom of the sliding block 18. A connecting rod 20 is installed at the top of the sliding block 18. An engaging block 21 is fixedly connected to the outer surface of the connecting rod 20. The top end of the connecting rod 20 penetrates through the connecting plate 15 and a sealing plate 22 is installed. The sealing plate 22 abuts against the discharge chute 4 to close the discharge chute 4.

[0058] In this embodiment, the first elastic member 19 includes, but is not limited to, a spring, a pneumatic piston cylinder, etc., as long as it can satisfy the reset of the sliding block 18 after displacement, and the elastic force of the first elastic member 19 is completely sufficient to support the gravity of the sliding block 18.

[0059] In this embodiment, the displacement member 14 includes, but is not limited to, an electric telescopic rod, a cylinder, a hydraulic rod, a linear motor, etc., as long as it can drive the connecting plate 15 to move linearly up and down.

[0060] In this embodiment, the bottom of the treatment barrel 2 is of a curved surface structure, and the bottom of the inner wall of the outer shell 1 is also inclined, inclined towards the opening groove 6, which is convenient for discharging materials.

[0061] A support frame 9 is fixedly connected to the top of the outer shell 1. A stirring rod 10 is fixedly connected to the bottom of the support frame 9. The stirring rod 10 extends into the treatment barrel 2. A plurality of stirring blades 11 are arranged on the outer surface of the stirring rod 10. A driving motor 12 is installed on the outer shell 1. A transmission assembly 13 is installed between the driving motor 12 and the treatment barrel 2. The driving motor 12 drives the treatment barrel 2 to rotate through the transmission assembly 13 to achieve stirring. During stirring, the sliding sleeve 8 covers the outer surface of the filter screen 3 to block the filter screen 3.

[0062] In this embodiment, the transmission assembly 13 includes, but is not limited to, mechanical transmission mechanisms such as a belt and pulley, a chain and sprocket, a gear set, etc., as long as it can achieve the transmission between the driving motor 12 and the treatment barrel 2.

[0063] The transmission assembly 13 is two meshing gears. One of the gears is installed on the output shaft of the driving motor 12, and the other gear is installed on the outer surface of the treatment barrel 2.

[0064] A cavity 23 is formed inside the stirring rod 10. A telescopic rod 24 is slidably connected to the inside of each of one set of the stirring blades 11. A second elastic member 25 is sleeved on the outer surface of the telescopic rod 24. One end of the telescopic rod 24 extends into the cavity 23, and a scraping plate 26 is installed at the other end of the telescopic rod 24. First inclined surfaces 27 are arranged at opposite ends of the two telescopic rods 24. An auxiliary rod 28 is fixedly connected to the top of the sealing plate 22. The auxiliary rod 28 extends into the cavity 23, and a moving block 29 is installed at the top end of the auxiliary rod 28. Two symmetric second inclined surfaces 30 are arranged at the bottom of the moving block 29.

[0065] In this embodiment, the second elastic member 25 includes, but is not limited to, springs, elastic tendons, piston cylinders, etc., as long as it can satisfy the reset after the displacement of the telescopic rod 24.

[0066] As the auxiliary rod 28 moves downward, the moving block 29 will move downward, and thus the first inclined surface 27 is squeezed through the second inclined surface 30, causing the two telescopic rods 24 to extend outward, and further enabling the two scraping plates 26 to move away from each other and closely adhere to the filter screen 3.

[0067] In this embodiment, the device has four usage states, which are specifically shown as follows:

[0068] Stirring state (please refer to Figure 5 a): Introduce the fluorine-containing wastewater into the treatment barrel 2, and put the carboxymethylated chitosan-based magnetic adsorbent into it. Then, drive the treatment barrel 2 to rotate through the drive motor 12, so that the stirring rod 10 stirs inside the treatment barrel 2, enabling the fluorine-containing wastewater to fully react with the carboxymethylated chitosan-based magnetic adsorbent, removing fluoride ions in the wastewater and generating precipitates;

[0069] Solid-liquid separation state (please refer to Figure 5 b): After the fluorine-containing wastewater and the carboxymethylated chitosan-based magnetic adsorbent have fully reacted, then through the contraction of the displacement member 14, the connecting plate 15 drives the support sleeve 16 to move downward, so that the sliding sleeve 8 drops and no longer blocks the filter screen 3. At this time, as the drive motor 12 drives the treatment barrel 2 to rotate, the precipitates and the purified water will be centrifugally separated. The water is thrown out and discharged through the drain groove 5, while the precipitates remain inside the treatment barrel 2;

[0070] Precipitate discharging state (please refer to Figure 5 c): Through the further contraction of the displacement member 14, the connecting plate 15 moves downward. When it touches the connecting block 21, it drives the connecting block 21 to move downward, so that the connecting rod 20 moves downward, and further enables the sealing plate 22 to move downward, opening the discharge slot 4, so that the precipitates are discharged from the treatment barrel 2 and then cleaned out through the opening slot 6;

[0071] Filter cleaning status (see Figure 5 d): Through the further contraction of the displacement member 14, the connecting plate 15 continues to move downward, thereby driving the connecting block 21 to continue to move downward, and the sealing plate 22 to continue to move downward, so that the auxiliary rod 28 moves downward, driving the moving block 29 to slide downward inside the cavity 23, and pushing the two telescopic rods 24 outward, so that the two scrapers 26 move away from each other and abut against the filter 3, and along with the rotation of the processing barrel 2, the sediment attached to the surface of the filter 3 can be cleaned up to avoid affecting the use of the filter 3.

[0072] The working principle of the fluorine-containing wastewater adsorption treatment device provided by the present invention is as follows:

[0073] Fluorine-containing wastewater is introduced into the treatment barrel 2, and adsorption material is added thereto, so that the fluorine-containing wastewater and the adsorption material react fully, fluoride ions in the wastewater are removed and precipitation is generated; then, the displacement member 14 contracts, so that the connecting plate 15 drives the support sleeve 16 to move downward, so that the sliding sleeve 8 falls, and the adsorbed wastewater and sediment are separated through the filter screen 3, and the water is discharged through the drainage groove 5, while the sediment remains in the treatment barrel 2, and then the displacement member 14 contracts again, so that the connecting plate 15 moves downward, and when it contacts the connecting block 21, it drives the connecting block 21 to move downward, so that the connecting rod 20 moves downward, and then the sealing plate 22 moves downward, and the discharge groove 4 is opened, so that the sediment is discharged from the treatment barrel 2 and then discharged through the opening groove 6.

[0074] Compared with the related art, the fluorine-containing wastewater adsorption treatment device provided by the present invention has the following beneficial effects:

[0075] By putting fluorine-containing wastewater and adsorption material into the treatment barrel 2 for reaction, the fluorine element in the fluorine-containing wastewater is adsorbed into the adsorption material to produce a precipitate. After static sedimentation, the wastewater and the precipitate can be separated by the contraction of the displacement member 14, and the precipitate can be discharged by contracting again. The reaction, precipitation and discharge functions are integrated into one, which greatly reduces the cost of use, reduces the floor space, facilitates discharge, reduces the workload of the staff, and realizes the conversion between different states. The operation is simple and convenient, and it has the effect of multi-functional use.

[0076] Second embodiment

[0077] Please refer to Figures 6-7 Based on the fluorine-containing wastewater adsorption treatment device provided in the first embodiment of the present application, the second embodiment of the present application proposes another fluorine-containing wastewater adsorption treatment device. The second embodiment is only a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the independent implementation of the first embodiment.

[0078] Specifically, the difference of the fluorine-containing wastewater adsorption treatment device provided by the second embodiment of the present application lies in that a water collection tank 31 and a suction pump 32 are fixedly connected to the right side of the outer shell 1. A first connecting pipe 33 is communicated between the water collection tank 31 and the inlet of the suction pump 32. The outlet of the suction pump 32 is communicated with a second connecting pipe 34. The second connecting pipe 34 penetrates through the outer shell 1 and extends to the inside of the outer shell 1. A spray head 35 is installed on the second connecting pipe 34. A conduit 36 is communicated between the drainage groove 5 and the water collection tank 31.

[0079] Compared with the related art, the fluorine-containing wastewater adsorption treatment device provided by the present invention has the following beneficial effects:

[0080] The water discharged through the drainage groove 5 can be introduced into the inside of the water collection tank 31 through the conduit 36, and through the suction of the suction pump 32, the water is sprayed out through the spray head 35, and the spray head 35 is aligned with the filter screen 3. As the treatment barrel 2 rotates, the filter screen 3 can be backwashed, thereby improving the cleaning effect on the filter screen 3.

[0081] The present invention also provides an adsorbent material, which is added to the above-mentioned fluorine-containing wastewater adsorption treatment device to realize the treatment of fluorine-containing wastewater. It is prepared from carboxymethyl chitosan and amino-functionalized magnetic nanoparticles.

[0082] Please refer to Figure 8 , the present invention also provides a preparation method of the adsorbent material for preparing the above-mentioned adsorbent material, including:

[0083] S1. Prepare carboxymethyl chitosan, and the steps are as follows:

[0084] S11. Place chitosan in a three-necked flask, add an organic solvent to dissolve and stir;

[0085] S12. Slowly add sodium hydroxide solution with a dropping funnel, and stir alkalinize in a constant temperature water bath;

[0086] S13. Dissolve chloroacetic acid in an organic solvent, slowly drop it into the alkalinized chitosan solution, and raise the temperature to continue stirring;

[0087] S14. Add glacial acetic acid to adjust the pH, pour the reaction solution into absolute ethanol and stir;

[0088] S15. Centrifuge and separate the precipitate, wash and dry to obtain carboxymethyl chitosan;

[0089] S2. Prepare amino-functionalized magnetic nanoparticles, and the steps are as follows:

[0090] S21. Dissolve substances containing divalent iron ions and trivalent iron ions in deionized water respectively to prepare solutions, and place them in a three-necked flask;

[0091] S22. Introduce nitrogen to exhaust air, and stir vigorously in a constant-temperature water bath;

[0092] S23. Rapidly add ammonia water dropwise using a dropping funnel, and continue stirring to obtain black Fe3O4 nanoparticles;

[0093] S24. Separate the Fe3O4 nanoparticles with a magnet, and wash them with deionized water until neutral;

[0094] S25. Disperse the washed Fe3O4 nanoparticles in absolute ethanol, and add a silane coupling agent or an amino acid-based substance;

[0095] S26. Carry out a reflux stirring reaction in a constant-temperature water bath;

[0096] S27. Separate the amino-functionalized magnetic nanoparticles with a magnet, and wash them with absolute ethanol;

[0097] S3. Prepare a carboxymethyl chitosan-based magnetic adsorbent, and the steps are as follows:

[0098] S31. Dissolve the carboxymethyl chitosan prepared above in deionized water to form a solution, and slowly add it to the solution prepared with an aluminum source substance, and stir evenly;

[0099] S32. Add the amino-functionalized magnetic nanoparticles prepared above, and ultrasonically obtain a uniformly mixed solution;

[0100] S33. Dissolve genipin in deionized water to form a solution, and slowly add it to the above mixed solution, and stir in a constant-temperature water bath;

[0101] S34. Add an alkaline solution to adjust the pH of the mixed solution, and continue stirring;

[0102] S35. Prepare a solution of polyethyleneimine with a mass fraction of 2%, and add it to the above mixed solution for stirring;

[0103] S36. Add 25% glutaraldehyde by mass fraction to the above mixed solution, and stir at room temperature;

[0104] S37. Wash the reaction product repeatedly with deionized water until the pH of the washing liquid reaches neutral, and separate the product with a magnet after each washing;

[0105] S38. Dry the washed product to a constant weight to obtain a carboxymethyl chitosan-based magnetic adsorbent, that is, the adsorbent material.

[0106] The organic solvent in S11 is one of isopropanol, methanol, ethanol, and acetone; the concentration of the sodium hydroxide solution in S12 is 40%-60%, the water bath temperature is 30-50°C, and the alkalization time is 1-2 h; the organic solvent in S13 is the same as that in S11, heated to 60-80°C, and the stirring time is 4-6 h; the pH in S14 is neutral; the centrifugation speed in S15 is 4000-6000 r / min, the centrifugation time is 10-30 min, and the washing is carried out 3 times with absolute ethanol.

[0107] The divalent iron ion substance in S21 is FeSO4·7H2O, and the trivalent iron ion substance is FeCl3·6H2O; the temperature in S22 is 80-100°C, and the stirring time is 30-60 min; the stirring time in S23 is 30-60 min; the silane coupling agent in S25 is one of γ-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and the amino acid substance is lysine; the temperature in S26 is 60-80°C, and the stirring time is 6-8 h; the washing with absolute ethanol is carried out 3 times in S27.

[0108] The aluminum source substance in S31 is one of aluminum nitrate nonahydrate and aluminum chloride; the ultrasonic time in S32 is 30-60 min; the constant temperature in S33 is 40-60°C, and the stirring time is 4-6 h; the alkaline solution in S34 is 1 mol / L sodium hydroxide solution, the pH is 8-9, and the stirring time is 6-8 h; the stirring time in S35 is 1-2 h; the stirring time in S36 is 6-8 h; the drying is carried out in a vacuum environment in S38, the temperature is 60-80°C, and the time is 60-90 min.

[0109] Further, the adsorbent is used for an adsorption experiment with fluorine-containing brine. The adsorbent and the fluorine-containing brine are mixed for adsorption, and the F - concentration in the actual fluorine-containing wastewater is reduced from 10.1 mg / L to 1.2 mg / L within 10 min. After 10 cycles, the adsorption capacity of the adsorbent for F - only decreases by 15.5%.

[0110] In this reaction, chitosan is used as a carrier to improve the structural stability of boehmite (AlOOH), and the hierarchical porous structure and polyethyleneimine groups of the carboxymethylated chitosan-based magnetic adsorbent shorten the adsorption equilibrium time. Through alkalization treatment, the hydroxyl groups (-OH) on the chitosan molecular chain are deprotonated to form negatively charged oxygen anions (-O -) Such oxygen anions have stronger nucleophilicity and can significantly improve the activity of subsequent carboxymethylation reactions. The oxygen anions on the alkalized chitosan attack the carbon atoms in chloroacetic acid molecules, and a nucleophilic substitution reaction occurs, successfully introducing carboxymethyl (-CH2COOH) onto the chitosan molecular chain, increasing the active groups on the chitosan molecule, providing more sites for subsequent reactions and interactions with other substances, and enhancing the reaction activity of chitosan.

[0111] Through amination modification, the ethoxy groups of γ-aminopropyltriethoxysilane (KH-550) are hydrolyzed to generate silanol groups (-SiOH), and the silanol groups undergo a condensation reaction with the hydroxyl groups on the surface of magnetite nanoparticles to introduce amino groups (-NH2) onto the particle surface. Genipin reacts with the amino groups in carboxymethyl chitosan molecules and the amino groups on the surface of aminated magnetic nanoparticles to form covalent bonds, crosslinking carboxymethyl chitosan and aminated magnetic nanoparticles together to form a stable structural framework. Hydroxyaluminum oxide (AlOOH) has a large specific surface area and abundant surface hydroxyl groups, and these hydroxyl groups can interact with target adsorbates such as fluoride ions, such as coordination and hydrogen bonding, thereby improving the adsorption capacity of the adsorbent for fluoride ions and the like. The loading of polyethyleneimine (PEI) increases the number of amino groups on the surface of the adsorbent, further improving the adsorption capacity of the adsorbent for certain anions (such as fluoride ions) because the amino groups can have electrostatic attraction with anions.

[0112] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural or equivalent process transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in other related technical fields, shall be similarly included in the patent protection scope of the present invention.

Claims

1. An adsorption treatment device for fluorine-containing wastewater, characterized in that, Comprising: A housing; A treatment barrel is rotatably connected inside the housing. The treatment barrel is used to hold fluorine-containing wastewater and put in an adsorbent material, so that an adsorption reaction occurs between the fluorine-containing wastewater and the adsorbent material. A filter screen is installed on the treatment barrel, and a discharge chute is installed at the bottom of the treatment barrel. A drain chute and an opening chute are arranged on the left side of the housing. A partition is fixedly connected inside the housing, and a sliding sleeve is slidably connected to the partition; A displacement member is fixedly connected to the bottom of the housing. The top end of the displacement member is fixedly connected to a connecting plate. A support sleeve is fixedly connected to the connecting plate. A cylinder is installed at the bottom of the housing. A sliding block is slidably connected inside the cylinder. A first elastic member is installed at the bottom of the sliding block. A connecting rod is installed at the top of the sliding block. An engaging block is fixedly connected to the outer surface of the connecting rod. The top end of the connecting rod penetrates through the connecting plate and is installed with a sealing plate. The sealing plate abuts against the discharge chute to close the discharge chute.

2. The fluorine-containing wastewater adsorption treatment device according to claim 1, wherein A support frame is fixedly connected to the top of the housing. A stirring rod is fixedly connected to the bottom of the support frame. The stirring rod extends into the treatment barrel. A plurality of groups of stirring blades are arranged on the outer surface of the stirring rod. A driving motor is installed on the housing. A transmission component is installed between the driving motor and the treatment barrel. The driving motor drives the treatment barrel to rotate through the transmission component to achieve stirring; during stirring, the sliding sleeve covers the outer surface of the filter screen to block the filter screen.

3. The fluorine-containing wastewater adsorption treatment device according to claim 2, wherein The transmission component is two mutually meshing gears. One of the gears is installed on the output shaft of the driving motor, and the other gear is installed on the outer surface of the treatment barrel.

4. The fluorine-containing wastewater adsorption treatment device according to claim 2, wherein A cavity is formed inside the stirring rod. A telescopic rod is slidably connected inside each of a group of the stirring blades. A second elastic member is sleeved on the outer surface of the telescopic rod. One end of the telescopic rod extends into the cavity. A scraping plate is installed at the other end of the telescopic rod. First inclined surfaces are arranged at opposite ends of the two telescopic rods. An auxiliary rod is fixedly connected to the top of the sealing plate. The auxiliary rod extends into the cavity. A moving block is installed at the top end of the auxiliary rod. Two symmetric second inclined surfaces are arranged at the bottom of the moving block.

5. The fluorine-containing wastewater adsorption treatment device according to claim 4, characterized in that, A water collecting tank and a suction pump are fixedly connected to the right side of the housing. A first connecting pipe is connected between the water collecting tank and the inlet of the suction pump. The outlet of the suction pump is connected with a second connecting pipe. The second connecting pipe penetrates through the housing and extends into the housing. A spray head is installed on the second connecting pipe. A conduit is connected between the drain chute and the water collecting tank.

6. An adsorbent material is added to the fluorine-containing wastewater adsorption treatment device according to any one of claims 1-5 to achieve the treatment of fluorine-containing wastewater, characterized in that, Prepared from carboxymethyl chitosan and amino-functionalized magnetic nanoparticles.

7. A method for preparing an adsorbent material for preparing the adsorbent material as described in claim 6, characterized in that, Including: S1. Prepare carboxymethyl chitosan, and the steps are as follows: S11. Place chitosan in a three-necked flask, add an organic solvent to dissolve and stir; S12. Slowly add a sodium hydroxide solution with a dropping funnel, and stir under constant temperature water bath for alkalization; S13. Dissolve chloroacetic acid in an organic solvent, slowly add it to the alkalized chitosan solution, and raise the temperature and continue to stir; S14. Add glacial acetic acid to adjust the PH, and pour the reaction solution into anhydrous ethanol and stir; S15. Centrifuge and separate the precipitate, wash and dry it to obtain carboxymethyl chitosan; S2. Prepare amino-functionalized magnetic nanoparticles, and the steps are as follows: S21. Dissolve the divalent iron ion-containing substance and the trivalent iron ion-containing substance in deionized water respectively to prepare solutions, and place them in a three-necked flask; S22. Pass nitrogen to exhaust air, and stir vigorously in a constant-temperature water bath; S23. Quickly add ammonia water dropwise with a dropping funnel, and continue stirring to obtain black Fe3O4 nanoparticles; S24. Separate the Fe3O4 nanoparticles with a magnet and wash them with deionized water until neutral; S25. Disperse the washed Fe3O4 nanoparticles in absolute ethanol, and add a silane coupling agent or an amino acid substance; S26. Carry out a reflux stirring reaction in a constant-temperature water bath; S27. Separate the amino-functionalized magnetic nanoparticles with a magnet and wash them with absolute ethanol; S3. Prepare a carboxymethyl chitosan-based magnetic adsorbent, and the steps are as follows: S31. Dissolve the carboxymethyl chitosan prepared above in deionized water to prepare a solution, and slowly add it to the solution prepared with an aluminum source substance, and stir evenly; S32. Add the amino-functionalized magnetic nanoparticles prepared above and ultrasonically obtain a uniformly mixed solution; S33. Dissolve genipin in deionized water to prepare a solution, and slowly add it to the above mixed solution, and stir in a constant-temperature water bath; S34. Add an alkaline solution to adjust the pH of the mixed solution, and continue stirring; S35. Prepare a 2% by mass solution of polyethyleneimine and add it to the above mixed solution for stirring; S36. Add 25% by mass of glutaraldehyde to the above mixed solution and stir at room temperature; S37. Wash the reaction product repeatedly with deionized water until the pH of the washing solution reaches neutral, and separate the product with a magnet after each washing; S38. Dry the washed product to a constant weight to obtain a carboxymethyl chitosan-based magnetic adsorbent, that is, the adsorption material.

8. The method for preparing the adsorption material according to claim 7, characterized in that, In S11, the organic solvent is one of isopropanol, methanol, ethanol, and acetone; in S12, the concentration of the sodium hydroxide solution is 40%-60%, the water bath temperature is 30-50°C, and the alkalization time is 1-2 h; in S13, the organic solvent is the same as that in S11, heat up to 60-80°C, and the stirring time is 4-6 h; in S14, the pH is neutral; in S15, the centrifugation speed is 4000-6000 r / min, the centrifugation time is 10-30 min, and the washing is carried out 3 times with absolute ethanol.

9. The preparation method of the adsorption material according to claim 7, wherein, In S21, the divalent iron ion-containing substance is FeSO4·7H2O, and the trivalent iron ion-containing substance is FeCl3·6H2O; in S22, the temperature is 80-100°C, and the stirring time is 30-60 min; in S23, the stirring time is 30-60 min; in S25, the silane coupling agent is one of γ-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and the amino acid substance is lysine; in S26, the temperature is 60-80°C, and the stirring time is 6-8 h; in S27, the washing with absolute ethanol is carried out 3 times.

10. The method for preparing the adsorption material according to claim 7, characterized in that, The aluminum source material in S31 is one of aluminum nitrate nonahydrate and aluminum chloride; the ultrasonic time in S32 is 30 - 60 min; the constant temperature in S33 is 40 - 60 °C and the stirring time is 4 - 6 h; the alkaline solution in S34 is a 1 mol / L sodium hydroxide solution with a pH of 8 - 9 and the stirring time is 6 - 8 h; the stirring time in S35 is 1 - 2 h; the stirring time in S36 is 6 - 8 h; in S38, it is dried in a vacuum environment at a temperature of 60 - 80 °C for 60 - 90 min.

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